Emulsifiable toxicant solution containing emulsifier of alkaryl sulfonic acid polyoxyalkylated polyamine salt



United States Patent l 3,298,912 EMULSIFIABLE TQXICANT SOLUTION CONTAIN- ING EMULSIFIER 0F ALKARYL SULFONIC ACID POLYOXYALKYLATED POLYAMINE SALT Oscar L. Scherr, La Mirada, Califi, assignor to Emery Industries, Inc., Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Oct. 2, 1963, Ser. No. 313,190 4 Claims. (Cl. 167-42) This invention relates to a toxicant composition adapted to be mixed with water by the agriculturaluser to form a stable emulsion adapted for spray usage. More particularly the invention brings to the composition a new emulsifying agent capable of giving instant dispersion or bloom when mixed with water of any degree of hardness, the resulting emulsion being a highly stable one.

This application is a continuation-in-part of co-pending application, Serial No. 37,546, filed May 31, 1960, now abandoned, which application, in turn, is a division of application, Serial No. 824,925, filed July 6, 1959, now abandoned.

The present practice of destroying or controlling insect, fungus, weed and other agricultural pest invasions on our agricultural areas by large scale spraying of the newer organic toxicants such as DDT, aldrin, dieldrin, toxaphene, malathion, parathion, esters of 2,4,5-trichloro phenoxyacetic acid and many others requires having concentrated solutions of the toxicants in suitable organic solvents such as xylene, kerosene, aromatic oils or isopropanol, together with an emulsifier of such power that when the toxicant concentrate is mixed in diluted solution with available water of whatever hardness, a stable oil-in-water emulsion is formed in which the toxicant solvent solution is finely dispersed. The resulting emulsion is a highly stable one and it may thus be sprayed over large areas without separating in the spraying rig tank even when held therein for many hours before being used.

Until recently many of the available emulsifiers for this purpose were blends of polyoxyethylated sorbitan esters, polyethylene glycol esters, glycol esters and petroleum sul-fonates, however, emulsifiers of this type did not give the instant aqueous dispersion, known as bloom, when the toxicant solvent concentrate was mixed with water. Some emulsifiers worked better in hard water containing 300 to 600 p.p.m. of CaCO others were better in Waters of less hardness, 50 to 125 p.p.m. The operators of insecticidal spraying companies were forced to stock many assorted emulsifiers for use with the various toxicants required. The present invention solves this problem by providing a novel anionic emulsifier which affords the most desirable bloom characteristics no matter whether the water employed be hard or relatively soft, this emulsifier normally being employed in conjunction with one or more nonionic emulsifiers in order to develop the optimum hydrophilichydrophobic balance in the composition.

More recently, US. Patent No. 2,696,453 introduced the use of calcium dodecylbenzene sulfonate as a substitute for the petroleum sulfonates in blends of emulsifiers containing nonionic polyoxyethylene ethers and esters. While this innovation gives finer dispersion and instantaneous bloom of the toxicant emulsions, the problem of producing emulsifiers that are effective over a wide range of water hardness is still not completely solved. Moreover, the inherent presence of water in the metal sulfonate (formed as an incident of the neutralization of the sulfonic acid portion of the molecule with the calcium reactant) causes decomposition of certain toxicants (e.g., tetraethyl pyrophosphate) as well as otherwise impairing the utility of the composition.

3,298,912 Patented Jan. 17, 1967 ice Applicant has found that anionic emulsifying agents made up of the salt of an oxyalkylated alkylene polyamine with a commercially available alkyl benzene sulfonic acid make excellent toxicant emulsions which are surprisingly effective over a much wider range of water hardness than has heretofore been possible.

The oxyalkylated polyamine component of the salt is one of the type formed by reacting an alkylene polyamine containing from 2 to 8 carbon atoms, and selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethyl pentamine and propylene diamine, with a C C alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide in the proportion of from two to three moles of the oxide for each mole of the polyamine. The products so formed, which can also be prepared by other conventional means, if desired, have a total of from two to three hydroxyalkyl groups each containing from two to four carbon atoms. For example, when ethylene diamine or diethylene triamine are reacted with from two to three moles of an alkylene oxide, products of the following general structure may be obtained:

where from two to three of the Rs represent C -C hydroxyalkyl groups and where the balance of the Rs are hydrogen atoms. The above structures are typical of those which are formed by reacting an alkylene oxide with an alkylene polyamine.

In'the preferred practice of this invention, the alkylene polyamine employed is selected from the group consisting of ethylene diamine and diethylene triamine, while the preferred oxyalkylating agent is propylene oxide.

The alkylbenzene sulfonic acid compound employed in forming the salt is one of the type commercially avail able for use in detergent formulations, the alkyl substituent group on the benzene containing from 8 to 18 carbon atoms. Representative alkyl groups, which may be branched or straight chain, are octyl, nonyl, dodecyl, tridecyl, hexadecyl and octodecyl. Preferred compounds are those wherein the alkyl group contains from 12 to 14 carbon atoms, as represented, for example, by dodecyland tridecylbenzene sulfonic acid.

The emulsifier hereof is formed from the oxyalkylated polyamine and the alkylbenzene sulfonic acid components by conventional methods adapted to provide the neutral salt. Methods of this character are fully set forth in Examples II, IV, VI and VIII, as given below.

The anionic emulsifiers of this invention are neutral salts having the following structural formula:

where the Rs represent alkyl groups of from 8 to 18 carbon atoms each and X is a bifunctional ammonium radical containing from 2 to 8 carbon atoms derived by oxyalkylation of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine or propylene diamine with from 2 to 3 moles of ethylene oxide, propylene oxide or butylene oxide. A typical salt, formed by neutralizing dodecylbenzene sulfonic acid with 3 4 N,N'-dihydroxypropylethylene diamine, has the following Example III.Ethylene diamine plus 2 mols structure: butylene oxide 540 grams (9 mols) anhydrous ethylene diamine were I CrHsOH CSHGOH O charged to the pressure reactor at 35 C. and then purged H2501, m, with dry nitrogen gas. 1296 grams (18 mols) of butyll H H H l ene oxide N (Uni-on Carbide) were added slowly from a pressure scale tank after first raising temperature of reactor (steam-jacketed) to 157 C. Total time for The new emulsifiers of the type described above when 10 addition Was 14 minutes- MaXimuIn 'tempel'ature used in combination with non-ionic emulsifiers and a mined Was maXimllm Pressure Was 150 P- toxicant and an organic solvent give clear, concentrated After reaction Was Complete. minutes after addition toxicant solutions which will not separate on storage. of bull/16116 OXide Completed) Pressure Was 25 P- and The nonionic emulsifiers employed are those which are temperature PPOdllCt was cooled C" and common in the trade, many products of this character 15 unloaded Product Obtained Was light colored Paste C011- being set forth herein in the examples. These mixtures, wining 1116 2 mol addition Product Yield Was 993% or solutions, are free of water, thus making for great sta- Of thfiOIeticaL bility on the part of the toxicants themselves. This is attributable to the fact that in neutralizing the sulfonic Examl IV acid, no water is formed as a product of neutralization,

with the result that the mixture is anh drous. The resence of even traces of water has been found to alfecl the of the Oxyalkylated amme pmpared m Example III were stability and shelf life of many toxicants, particularly Charged to 'a.stamless Steel beaker agitated 325 DDT and other chlorinated derivatives. grams. (1 llquwalent) a commtlrclal .doqecyl'belnzqne On dilution with water these emulsifier-toxi'cant mixu1fomc acld were added Slowly agltatlon tures give instantaneous fine dispersion, or bloom, and l temperature between 45 and by means of an form emulsions which are highly stable even after long we bath when an f Sulfom? acld had been added standing. Furthermore, the resulting emulsions remain the pH of a 1% Q isopropanol was found stable upon redispersion in the event any settling occurs to be Addltlonal anllne from Exanlp 16 III was after long standing or for other reasons. The emulsions added 1mm the PH was ralsed to This took 34'45 i 1.5 arms of a clear amber ve a lo de ree of foam when s ra in or handhn grams .yleld Was 53 e i cluality \i vhicl r also increases their effe ctiileness g hquld conlammg 8683% d1 (hydroxybutyl) ethylene diamine disulfonate.

70 grams isopropanol and 102.05 grams (1 equivalent) Example I.Ethylene diamine plus 2 mols 35 Exam 1 V propylene oxide p e In this operation, 927 grams anhydrous diethylene tri- 660 grams anhydrous ethylene diamine were charged amine were charged to the pressure reactor at 15 C. a Pressure reactor H1015) at P g fill and purged with dry nitrogen gas for two minutes. Temone minute with dry nitrogen gas. 1276 grams (22 40 peratu-re was raised to 150 C. using steam in the remols) 'of propylene oxide were added slowly from a presactors coil and jacket. 1044 grams of propylene oxide sure scale tank, after first raising the temperature of the were slowly added to the reactor with agitator on. After steam-jacketed reactor to 142 C. Total time for the 16 minutes the addition was complete, temperature was addition was 24 minutes, maximum temperature reached 185 C. and pressure 100 p.s.i. In 14 minutes more, was 186 C. and maximum pressure 125 pounds per reaction was complete, temperature was 165 C. and square inch. At end of reaction pressure dropped to 25 pressure 72 p.s.i. Product was cooled to 110 C. and p.s.i. Product was cooled to C. and unloaded. A unloaded. Yield was 99.5% of theoretical. Product yield of 1851 grams (95.6% of theory) of a water-white was a soft paste. This reaction proceeded, in the main, liquid which cooled to a soft paste was obtained, conin accordance with the following equation:

GHa-CHOH-CHZNHCH2CHzNH-CH2CH2NHCH2CHOH-CH taining 2 mols propylene oxide per mol of ethylene Exa mple VI diamine.

grams of JSOPI'OPEIHOI were charged to a stainless Example II steel vessel. 109.5 grams (1 equivalent) of the :oxyalkyl- 60 ated mine from Example V were added to the isopropanol 243 grams of Socal No. 2, an aromatic xylene type With stirring. 325 grams (1 equivalent) of a commercial solvent, were charged to a stainless steel beaker. 228 dodecylbenzene sulfonic acid were added'slowly with s'tirgrams (1.3 mols) of the oxyalkylated amine from Exring to the amine-solvent mixture. The temperature was ample I was then added to the solvent with stirring. 659 maintained between 4550 C. with the aid of an ice bath. grams (2.0 6 mols) of commercial dodecylbenzene sul- 5 When all of the sulfonic acid had been added, the pH of fonic acid were added slowly, keeping the temperature bea 1% solution of the mixture in 50% isopropanol was tween 45 and 50 C. by means of an ice bath. When found to be 3.5. Additional small amounts of amine all or the sulfonic acid had been added, the pH of a 1% were added to adjust the pH of the product to between 4 solution of the mixture in 50 isopropanol was found and 7. 15 additional grams of amine being required to to be 3.5. 10 grams additional Example I compound 70 raise the pH to 5.3. The yield was 519.5 grams of a were required to bring the pH up to 4.6. The yield was clear, amber liquid containing 86.5% of di(hyd-roxy- 1140 grams of a clear pale amber liquid. Analysis by propyl) diethylene triamine di-dodecylbenzenesulfonate. cationic titration showed the product to contain 71.5% It may here he noted that diethylene triarnine is conactive material (414 eq. wt.) which was the neutralization sidered a bifunctional amine for the purposes of these product of the oxyalkylated diamine and the sulfonic acid. compounds since at the pHs used for toxicant concen tr-ates, to 7, only the terminal primary amino groups are functional in forming salts.

Example VII The above results clearly demonstrate that toxicant Formula B,-which contained the 2 mol propylene oxide, ethylene-diamine adduct salt of d-odecylbenzene sulfonic acid in both hard and soft water, was comparable or 5 superior to the calcium salt in every particular. For exam- .T-he following example illustrates the use of. the ethyl- P16 in Water of 342 ppm hardness the bloom was the ene diamine-2 mols propylene oxide adduct salt of dodecyl- Same, and in the initial emulsification the product of the benzene sulfonic "acid in a 4 Pound "chlordane P gallon invention was slightly better. After 1 hour, the calcium emulsifiable concentrate. .Two Formulas A and B were salt began to cream and oil began to separate After the prepared- 10 same period, the product of the invention showed only a EMULSIFIABLE CONCENTRATE trace of. crea rning and no oil separation. After 20 hours, the calcium salt had separated 4 ml. of oil, while the ing fi t i vent-ive product showed only 2 :ml. of cream. After redisk g gg 50 persion, the calcium salt emulsion showed poor stability E 1 ff f and separated immediately. The product of the invention mu s1 er (based on Ca) 5 h d 11 Formula B: s owe exce ent sta 1ty on re ispersion.

Chlordane 45 Kerosene 50 Example V Emulsifier (present invention) 5 In this operation 208 g. (1.18 mols) of the ethylene diaanine-Z mols propylene oxide adduct of Example I- In each of the above formulations, 0f the emulsl were dissolved in 138 g. of isopropanol. To the solution fief p Was made p the 's of was then slowly added commercial dode-cylbenzene sulconve'ntlonal emulsifiers wherein all p the P PY fonic acid, the temperature being controlled at 4550 C. amine sul-fonate (anionic) are nonionic in character: by use o-f'an ice bath. The pH of the solution was then adjusted to 4.8 :by addition of 20 g. of the amine-propylene Pflcent oxide adduct, and to this solution was added 73 g. of iso- Isopmpyl 5 propanol. The resulting product, which was a clear, flow- Dodcylphen9l'ethylene 07nd? adduct 6 able amber liquid, was found by cationic titration to on- Propylene oxldeethylene oxlde adduct 27 3Q tain 75 of active material (414 eq. wt.) Ethoxylated nonylphenol 6 The product prepared as described above was then Polyoxyethylated mlxed fatty W011: ands 5 used to prepare an emulsifiable toxicant concentrate which Xylene was then tested in hard and soft waters much as described in the recedin exam le. The erformance of this ma- In Formula A the balance the enmlslfier.was made terial i record d in Table II bglow along with that of up of calcium dodecylbenzene sulfo-nate, while in Formula other Compositions which varied 0 n1 y in the amine amine B the l the emulsifier i up propyl' alkylene oxide adduct or metal used to neutralize the em oxide (2 molww'ethylenfa 9 (1 mol) adduct snlfonic acid. Specifically, .all these compositions, apart gf figizi gg g ajigfigf ggg g f ggiigg 5 m1 from the dodecylbenzene sulfonic acid salt components of the emulsi-fiable concentrate were added to 95 ml. of 40 recited m Table were Prepared as follows hard Water (342 P- in one Case and to 95 soft 22.0 g. of the above or other dodecylbenzene sulfonate water 34 p.p.m.) in the other, as contained in stoppered salt; graduated cylinders. At this point observations were re- 121 DDT; corded as to the nature of the bloom. Each cylinder 36.4 g naphtha Solvent; was then up-ended 20 times, after which the resulting 5'0 isopropanol; emulsions were observed first to determine their initial 225 of a mixture of emulsifiers prepared as follows: characteristics and then their stability at intervals over a 20-hour period. Lastly, at the end of the 20-hour obser- G, vation period the emulsions were redisperse-d by mild shak- 'Mi d monod dii l amine 1- ing of the cylinder, following which note was made of the forums 22.0 redispersal characteristics of each system and of its foam- Meth y polyoxyethylene-polyoxypropylene inlg qualities. The results of all these tests are reported glycol 1.5 in Table I below, the symbol S being employed in said N l h p l ethylene glycol 15.0 table to designate the highest (and usually the only com- 5 C t il lyoxyethylene glycol 150.0 mercially acceptable) rating, followed in descending orde Aromatic solvent 9.0 of performance characteristics by E, G and F. A creaming tendency, represented by the indicated number of 5 ml. of the foregoing concentrate was then added to 95 milliliters of CR formed, represents an undesirable, ml. of hard water (229 p.p.m.) and in some cases to soft transitionary state .between a stable emulsion and one water (34 p.p.m.), following which tests were made and which has broken down at least in part to water and oil. observations recorded all as outlined above in Example The formation of oil is indicated as such. VII.

TABLE I Formula Bloom Init. Emul. M1. Cream fltaedisp Il'flgt. foartn a G1 1 Rating Ratmg 5 min 15 min 1 hr. 20 hrs a mg ag (A) Hard S E 0 0 "3111. Nil. it; ifiia; .9 n- 3 ififtijii: it? (B) Soft"- E G o 0.. lcr N11.

TABLE II I Ml. Cream Amine or Metal Used to Neutralize Water Init. Init. Redisper- Foam, ml.

the Sulionic Acid Hardness Bloom Emul. sion in p.p.m. min 15 min. 1 hr. 20 hrs Calcium (as calcium dodecyl ben- 229 5 zene sulfonate).

Do 34 Ethylene diamine plus dodecyl ben- 229 10 zene sulfonate-no alkylene oxide. Ethylene diamine plus 1 ethylene 229 4 oxide.

1 i l diamme plus 2 ethylene 229 8 Ethylene diamine plus 2 propylene 229 Nil oxides.

D0 34 Nil Ethylene diamine plus 3 propylene 229 Nil oxides.

Do 34 7 Ethylene diamine plus 2 butylene 229 1 oxides.

D0 34 2 Ethylene triamine plus 2 propylene 229 Nil oxides. Diethylene triamine plus 2 pro- 34 Nil pylene oxides. Diethylene triamine plus 3 pro- 229 S S 0 0 0 0 S Slight pylene oxides.

Do 34 S E 0 Tr cr. 2% cr 2 cr S Slight As shown in the above table, the products based on the emulsifiers of this invention, wherein the polyamine portion of the molecule is substituted with from 2 to 3 hydroxyalkyl groups, gave results which were essentially equal or superior to those obtained using the corresponding calcium sulfonate salts. On the other hand, those polyamine sulfonates which either contained no hydroxyalkyl or but one such group attached to the polyamine portion of the molecule, gave completely unsatisfactory results. Thus, the compounds formed from the nonoxyalkylated ethylene diamine and from ethylene diamine substituted with but a single hydroxyethyl group exhibited po'or bloom and initial emulsion characteristics. Moreover, they rapidly developed cream and oil and had relatively poor redispersal qualities. Other work, here unreported, shows that the optimum qualities of the present emulsifiers also tend to fall off rapidly as the polyamine portion of the sulfonate salt is substituted with more than 3 hydroxyalkyl groups, the salt formed from tetrahydroxyethyl-ethylene diamine, for example, having poor initial emulsion characteristics and developing 4 ml. of cream after :but minutes time.

Toxioant compositions or concentrates, adapted to readily form an emulsion upon the addition of water, are formed by the incorporation of the desired toxicant with the emulsifier compositions whether the toxicant be an insecticide, herbicide, plant hormone, fungicide, or the like. Such toxicant compositions advantageously contain one or more toxicants, the emulsifier proper, and an organic solvent or mixture of solvents, with or without various supplemental agents, so that all that it is necessary for the ultimate user to do is to disperse the composition in the requisite amount of water and spray or otherwise apply it to the surface to be treated. The proportions of toxicant used in such toxicant compositions are variable within wide limits although, in the usual case, the toxicant in the concentrate will range from about to about 50%. The amount of organic solvent will, in general, range from about to 60%, and the emulsifier composition will usually be present in proportions of about 5% to about 10%. The organic solvent or mixtures may be selected from a large group, typical examples of which are kerosene, 2-methyl-pentanediol-1,2, benzene, toluene, polymethyl naphthalenes, pine oil, and the like. The dilution with water to form the emulsions for spraying or the like may vary within wide limits so that, for example, ultimate emulsions may be made containing from a fraction of one percent to several percent, for instance, 5%, of the toxicant or mixture of toxicants.

I claim:

1. In an emulsifiable toxicant composition comprising an organic solvent, a toxicant, and at least one polyoxyalkylene ether nonionic emulsifier, the improvement comprising an oil soluble anionic emulsifier made up of the salt of a C C alkyl-substituted benzene sulfonic acid and a polyamine compound selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and propylene diamine, wherein a total of from two to three C -C hydroxyalkyl groups are attached to the nitrogen atoms of said polyamine.

2. The composition of claim 1 wherein there is also present an anionic emulsifier made up of mixed monoand diisopropyl amine sulfonates.

3. The composition of claim 1 in which the oil-soluble anionic emulsifier comprises the salt of d-odecylbenzene sulfonic acid and a compound of ethylene diamine wherein a total of from two to three C -C hydroxy alkyl groups are attached to the nitrogen atoms of said diamine.

4. The composition of claim 1 in which the oil-soluble anionic emulsifier comprises the salt of dodecylbenzene sulfonic acid and a compound of diethylene triamine wherein a total-of from two to three C -C hydroxy alkyl groups are attached to the nitrogen atoms of said triamine.

References Cited by the Examiner UNITED STATES PATENTS 2,731,338 1/1956 Fike et al 167-42 2,778,814 1/1957 Behrens 260-501 2,796,429 6/1957 Kreps 260-501 2,828,334 3/1958 DeGroote 260501 2,832,716 4/1958 Cassil 16742 2,862,848 12/1958 Keenan 167-42 2,898,267 8/1959 Lindner 16742 2,943,109 6/1960 Ramsay 260-501 FOREIGN PATENTS 529,038 8/1956 Canada.

LEWIS GOTTS, Primary Examiner.

ELBERT L. ROBERTS, Examiner.

R. HUFF, Assistant Examiner. 

1. IN AN EMULSIBIABLE TOXICANT COMPOSITION COMPRISING AN ORGANIC SOLVENT, A TOXICANT, AND AT LEAST ONE POLYOXYALKYLENE ETHER NONIONIC EMULSIFIER, THE IMPROVEMENT COMPRISING AN OIL SOLUBLE ANIONIC EMULSIFIER MADE UP OF THE SALT OF A C8-C18 ALKYL-SUBSTITUTED BENZENE SULFONIC ACID AND A POLYAMINE COMPOUND SELECTED FROM THE GROUP CONSISTING OF ETHYLENE DIAMINE, DIETHYLENE TRIAMINE, TRIETHYLENE TETRAMINE, TETRAETHYLENE PENTAMINE AND PROPYLENE DIAMINE, WHEREIN A TOTAL OF FROM TWO TO THREE C2-C4 HYDROXYALKYL GROUPS ARE ATTACHED TO THE NITROGEN ATOMS OF SAID POLYAMINE. 